Insecticidal compositions containing dodecachlorotetrahydro-4,7-methanoindene and method for combating noxious organisms therewith



March 2, 1954 E. E. GxLBERT 2,671,043

INSECTICIDAL COMPOSITIONS CONTAINING DODECACHLOROTETRAHYDRO-4,'-METHANOINDENE AND METHOD FOR COMBATING NOXIOUS ORGANISMS THEREWITH Filed April 6, 1951 II-O 7o 8.o wAvE LENGTH /N M/c'RoNs SPECTROGRAM oF DoDEcAcHLoRoTET/AHYDRO-4, 7-METHANo/NDENE -A= REACTION PRODUCT 0F DECACHLOROTETRAHYDRO-4, 7METHANOINDENEONE AND PCI5 B= REACTION PRODUCT OF HEXACHLOROCYCLOPENTADIENE AND AIC/3 C= CARBON D/SULPHIDE SOLVENT ooo oo ooo gmcozgwwmw` No/ss/wSNvzLL .LNJId INVENT0R- EVERETT E. GILBERT ATTORNEY.

Patented Mar. 2, 1954 UNITED STATES PATENT oFEicE 2,671,043 1N SECTICIDAL COMBO SITION S CONTAIN- fIN G DODECACHLOROTETRAHYDBQQ-g'- METHANOINDENIE AND METHOD FOR ICOM'BA'TIN G THEREWITH N (DXIO'U S 0R GAN'ITS Everett E. Gilbert, llilnshing, N. Y., assigner to Allied Chemical & -Dye Corporation, New York,

Y., a corporation of New 'York Application April 6, 1951, Seria1N0.`2'19,'740

sation of hexachlorocyclopentadiene With AlCla isshown as solid line B while the carbon disulfide solvent appears as solid line C. The-two spectrograms are substantially identical, hence the `,productsprepared by the two processes'are identical.

Dodecachlorotetrahydro4;7methanoindene is e. white crystalline solid which sublimes without smelting at temperatures above about `240" C., soluble in benzene. acetone, kerosene and carbon tetrachloride, etc., and while virtually insoluble in methanol, is appreciably soluble in 'the lower .aliphatic alcohols having 2 or more :carbon atoms, particularly at elevated temperatores. .,Itphas high-toxicity egainstmany dimpurely :controllable ynoxious organisms insects and their `iaryae @f $1.1@ OJSQS :lie-m9@ tera (mothsr Qoleoptera (beetles), Qrthoptere (grasshoppers), etc.

The compositions of my invention oompitisees che essentiel toxic .iperediept dodecechlcioietrphydro-"figY-,ipetheiioipdepe iie. bexechloiccyo'iopentadiene dimer, which may `be applied alone or in association with a uid or solid carrier matergial in any suitablefmanner adapted 1.13.0 combat the particular organism to pe copti'olled.- For application os a fluid ,spicy ores impregnati@ the solid dodecachlorotetrahydro-4,7methano indene may yconveniently be dissolved or Adispersed in any standard "liquid carrier, such as kerosene o1' the like. .For implication vas e dest Aor spray powder, it may he lipped or .nillled with e suitable iipely `divided 1d materiel, such es clay or the like, together suitable odievcriis, such es wetting 'epd' dispersirig agents epticeliipg agents, aritidiistipe agents, etc-if desired. It may 4readily tbe applied trom sciiitioii 'in Solvents 'in which it sclliiblerfor eioilipe acetone, xylepe, and aromatic epd eiippetic Vpeticleiiiii solvents., or in mixtures or 'emulsions of such solvents with water orrikerosene, together with suite-ble emulsiiyiiic agents Applicaties of dodecechlorotetreiydio-457 'methanoindeiie in liquid solution 'form or emulsion ,form fespeoially .adapted to mothfprooiips of fabrics 'epd the like, while application iii the'icrip of wettaple powders, or iiiiidfspreys 'die form of solutions, vdispersione emidsioris 'or 'die 'ilikeriiiay conveniently be used in its application to veeetebie crops.

The Yooneeioiratioii of dodececlilcroieirehydro- 4,7-meihcpciiideiie .will very somewhat With-tile type of composition, with the organism to tbe controlled epd with surrounding 'field' 'conditions general, surprisingly 10W concentra.- tiops ci vtoxiiiaiit in :my pew ccippcsitiops sive eective 'irisecticidel A.control inmoiiy ceses es "n: dicated inthe ifol'lowing tables. composietions, however, will lpreierably contain at least about 0.5% of dodecachlorotetrahydro 4,7- rnethanoindene --based on. -the solids content. foi the compositions. sua-lly concentrations, :between aboutv.0;5% aand about ,310% :are satisfactory. These compositions may-be.dilutedsome- -whot in application es .indicated in the tables,

especially in the case of the Wettable spray powders; and doses applied will vary according to the vparticular organisms to be controlled, eld

. 4 dane. In carrying out the tests, separate areas in a eld of red clover were sprayed on July 19, with suspensions in water of wettable spray powders containing dodecachlorotetrahydro 4,7-

(abbreviated as DTM in the table) and a small 5 methanoindene and chlordane respectively, amount of a wetting agent, and dispersing the similar to those described above and allowed to resulting wettable spray powder in water in stand until August 6 when cages containing 50 the proportion of one pound of powder per 100 grasshoppers were placed over four square feet of gallons of water. After dipping, the leaves were each of the treated areas and over a like untreated withdrawn, and, in the rst of the two tests, were 10 area. The percent dead ve days after exposure dried three hours and then five 6th instar larvae 'to the treated clover in each case is shown in were confined on the treated plants. Results Table III below: hfwtpercent of larvae dead four days after m' Table IIL- Effect of dodecachlorotetrahydro-4,7- eilelosr'cond test was Carried out in the Same 15 methanoindene on grasshopper infestations oc- TT. manner, except that plants were allowed to stand C@ mg 17 days after application to foliage two days after dipping before infestation with N larvae in order to determine the residual toxicity Treatment obo per No Alf@ Perg F dm of the toxicant. acre) Hoppers After 51 "e g The results are indicated below: 20 Days Table I.-Toscicity of dodecachlorotetrahydro- DTM, 25% 4# so 9 a2 sughi.

4,7 methanoiudene to armywoms Chlordalle, 20% 5#. 50 34 32 Cgllrllete defonoheck (no mxicaiic) so 4s 4 DOI Insect Dosage Toxicant Pelnt In Table IV below are shown the results of a test in which 20 x 20 ft. plots of grass were treatsollthemamwmm" %s;a$e9d}s-amenable 1 ed with duets comprising 5% cmordane and 5% Do %1b. per ldgals as wettable 100 dodecachlorotetrahydro 4,7 methanoindene re- Spfay pow er* 3,0 speciively, with 95% clay, at the rate of 1/2 pound of active material per acre. Fifty grasshoppers ,Table II below 'Shows the results of fiek; tests were caged over four square feet of each plot of Wth .dodecachlootetfhydro'4J7'me1han0mdere treated grass within a few hours after treatment. on grsshoppers mfeistmg red. clover m compan' Table IV shows the number and percent of grassson wlth a commercial chlorinated hydrocarbon ,35 hoppors dood after four doyo Y f'chlordane recommended as highly toxic to grasshoppers. In carrying out the tests, 1290 Table IV.-E1ect of dodecacblorotetrahydro4,7 sq. ft. of clover, infested with three species of methanomdene'on mfestafwns 0f grasshoppers gmsshoppor @oo loggod! Melanopzus man on grass occurring immediately after treatment rubrum; lesser migratory, Melanoplus mexicanas ,4o and the two-striped Melanoplus bioittatus, the T tm t NO H0p NX.ftDed Percent vdominant species being the red-legged), was rea e pers Dfgs Dead sprayed with a suspension prepared by mixing clay and dodecachlorotetrahydro4,7meth2in0 DTi/1,5%Dusi 50 43 se indem, in the proportion of three parts clay to glloit Dlt-m Sg 7g one part dodecachlorotetrahydro-4,7-methanoe@ Ca indene, with a small quantity of a wetting agent and dispensing the resulting Wottable Spray poW In Table V below are shown the results of tests dorm Water in proportion of four pounds of the of the residual activity of the dodecachlorotetra- 'powder (one pound active toxicant) in 100 gal- 135' dm'qg'nlethanolpdene 1n comparlson Wlth lons of Water. The chlordaneii composition was chlordane. In thistest, 50 fresh grasshoppers 'propaed and applied in the same marmol., eX were caged over portions of grass treated as in- .cept' that'the powder contained four parts of clay heated for the testpf Table IV'. four days. after and one part of chlordane and was dispersed in treatment- Appfoxlma'tely one mch 0f ram feu Water in the proportion of vo pounds of powder the day before the infestation with grasshoppers. to 100 gallons of Water to produce the Same oro- 55 The table shows the number and percentage dead portion of toxicant per 100 gallons of water. four days after mfestatlon- Table II ShOWS the percent reductml in grass- Table V.Residual activity of olodecachlorotetrahODDBI population in the infested area after the hydro-4,7-methanoindene against grasshoppers indicated number of days. on grass Table II .-Percent redaction in grasshopper pop- D 1 alation on clover after treatment with dodeca- NO Hop- No' @ad Per' chlorotetrahydro-4,7-methanoindene Treatment Pers Ang; 133121 DTM,5 D i 5o 12 24 Percelllpliggtr(lgafper Chlordal, sDuStm. 50 10 20 Treatment Check (no toxicant) l. 50 0 D In Table VI below are shown field laboratory DTM 25% 4# 4 1 95.5 9M 94A 6 7 160 tests of dodecachlorotetrahydro-4,7-methanoin- Glilordane, 20% 5# 96.4 98.9 99.5 96.7 97.6 96.5 10 dene against grasshoppers in comparison with chlordane and toxaphene, the latter being a Table III below shows the results of field tests chlorinated camphene product. In these tests, carried out to determine the residual effectiveness cranberry bean plants were dusted with composiof dodecachlorotetrahydro4,'lmethanoindene 75 tions containing 3% chlordanef toxaphene against grasshoppers incomparison with chlorand dodecachlorotetrahydro-4,7metl1anoindene,

saisis Melanoplus feniarrubrm speciesl collected in the field, wereccnfinedto the treated pla-nts'lby means of 6" spherical 16 mesh screen-,cages and allowed to feed. Table VI shows the mortality of the grasshoppers after 1, 2, 3, 4 and 5 days on plants subjected to varying dosages of the several toxicants. Foliage consumed by grasshoppers was about equal with DTM and chlordane- Significantly more feeding occurred on toxaphene dusted plants.

i ses 5. An insecticidal wettable spray powder adapted for the control of insects of the order of Orthoptera comprising a mixture of at least about 0.5% of dodecachlorotetrahydro-4,7meth anoindene, an inert dust insecticidal adjuvant as Table VI .-Toic eect of dodecachlorotetrahydrO-4J-methanondene and two commercial grasshopper tomicants against grasshoppers in field laboratory tests on cranberry bean plants Dust No Percent Kill of Hoppers Atter- Treatment Charge, Hopp'ers Mig' 1 day 2days Bdays 4days days 25 6 g 10g. 5 40. 0 93. 3 5 6 DTM' 3% Dust 103 e o. o s3. 3 10o 200 6 0 100 6 0. 0 6. 7 26. 6 53. 3 93. 3 Chlofdane 3% Dust- 13g 833 g2g i 33 :3:13: 200 6 50. 0 83. 3 83. 3 100 25 6 0. 0 0. 0 6. 7 6. 7 40. 0 Toxaphene 133 32:3 133'3 ll l :331:: 200 6 100 Check N011@ 18 5. 5 11. l 11. l 16. G

The effectiveness of the dodecachlorotetrahydro-4,7methanoindene against carpet beetle larvae (Attagenus piceus Oliv.) whose damage is commonly referred to as moth damage is indicated by the following tests carried out according to ASTM method D-582-49T, entitled Tentative Methods of Tests for Resistance of Textile Fabrics and Yarns to Insect Pests, published in ASTM Standards for 1949, Part V, pages 12S-134. In the rst test, a 2.28% deposit of dodecachlorotetrahydro-4,7methanoindene applied to wool from a 1% acetone solution followed by drying, resulted in 100% kill of carpet beetle larvae allowed to feed thereon within a two weeks exposure period, with 91.8% protection to the fabric, i. e. with only 8.2% loss of weight of the original cloth swatch from feeding of the larvae.

In a second test, the same swatch, with no further treatment, retested with fresh larvae after eight months storage, again exhibited 100% kill and 95% protection against the larvae indicating no loss of toxicity on storage.

A test similar to those described above was run in which 1.3% of dodecachlorotetrahydro-4,7 methanoindene was deposited on wool from a 0.5 acetone solution. After eight months storage, the treated wool was exposed to carpet beetle larvae as before. 100% of the larvae were killed, the deposit effecting 97% protection of the wool.

While the above describes the preferred embodiments of my invention, it will be understood that departures may be made therefrom within the scope of the specification and claims.

I claim:

1. A new insecticidal composition comprising dodecachlorotetrahydro-4,7-methanoindene and an inert insecticidal adjuvant as carrier for the insecticide.

carrier for the insecticide and a wetting agent.

6. An insecticidal wettable spray powder suspension adapted for the control of insects of the order Orthoptera comprising a mixture of at least about 0.5% of dodecachlorotetrahydro-L7-methanoindene and an inert dust insecticidal adjuvant as the carrier for the insecticide suspended in an inert liquid insecticidal adjuvant as the carrier for the insecticide.

7 A method for controlling insects which comprises contacting said organisms with a composition containing as the essential toxic ingredient, dodecachlorotetrahydro-4,7methanoindene.

8. A method for controlling grasshopper infestations on field crops which comprises contacting grasshoppers with a composition containing as the essential toxic ingredient, dodecachlorotetrahydro-4,7-methanoindene.

9. A method for controlling carpet beetle damage on Wool which comprises impregnating the Wool with a composition containing as the essential toxic ingredient, dodecachlorotetrahydro- 4,7-methanoindene.

10. A method for controlling grasshopper infestations on field crops which comprises applying to the crops a dust comprising between about 0.5% and about 30% of dodecachlorotetrahydro- 4,7methanoindene and an inert dust insecticidal adjuvant as the carrier for the insecticide, at the rate of between about 1/8 lb. and about 1 lb. of toxicant per acre.

11. A method for controlling grasshopper infestations on field crops which comprises applying to the crops a liquid suspension comprising between about 0.5% and about 30% of dodecachlorotetrahydro 4,7 methanoindene based on the solid content of the composition and an inert 7 dust insecticidal adjuvant as the carrier for the insecticide suspended in a liquid nsecticidal ad- .iuvant as the carrier for the insecticide at the rate of between about 1,/8 pound and about 1 pound toxicant per acre.

V12. A method for controlling grasshopper in- Iestations on eld crops which comprises applying to the crops a liquid suspension comprising between about 0.5% and about 30% of dodecachlorotetrahydro 4,7 methanoindene based on the solid content of the composition and an inert dust insecticidal adjuvant as` carrier for the insectcide, suspended in water. Y l

EVERE'I'I' E.,GILBER.T;. y

References Cited in the ie of this patent UNITED STATES PATENTS OTHER REFERENCES Journal. American Chem. Society, 71, page 954,

March 1949. 

1. A NEW INSECTICIDAL COMPOSITION COMPRISING DODECACHLOROTETRAHYDRO-4,7-METHANOINDENE AND AN INERT INSECTICIDAL ADJUVANT AS CARRIER FOR THE INSECTICIDE. 